Azo-dyestuffs



Patented Dec. 20, 1949 UNITED STATES PATENT OFFI-(IE AZO-DYESTUFFS Ot o Kaiser, Dcr a h an Ray nd est Basel, Switz erland,,assignors to Qiba Limited, Basel; Switzerland, aSwiss firm Nollra yingn Application August '28,". 1947, Serial No. 721,138. In SwitgerlandSeptember 11, 1 946.

12 cla msv (Cl. 260-175 In U. s. Patents Nos. 1,594,828 and 1,782,682"

are described asymmetrical urea derivatives of monoazo-dyestuffs which dye cellulose fibers yellow tints. These dyestuffs are made by treating,

in which R1 represents a naphthalene radical.

which is attached to the azo-group in an 04113051. tion and contains at least one sulfonic acid group, but otherwise is free from auxochromic groups, R2NH- represents the radical of an amine of the benzene or naphthalene series coupled in para-position With respect to the amino-group, and

coon

represents the radical of a 4-amino-4-hydroxy-. 1:1-azobenzene-3'-carboxylio acid, are obtained by treating with phosgene monoazo-dyestuffs of the formulae R1. :.Na and R1.-N==N-.-Ra--NH 2 used as starting materialsare advantageously 0h.

tained by diazotizing an c-naphthylamine sulfonic acid and coupling the resulting diazoecom= pound with an amine capable of coupling in the;

para-position, that is to say, a so-called middle component, the coupling being advantageously ndu e n idm dium f r exam le a m d um r n ere a d with a et c acid. As. diam:

components in this connection there come into consideration a-naphthylamine monosulfonic acids such, for example, as l-amino-naphthalene-3-., 4-, -5-, -6- or -7-sulfonic acid, but more especially a-naphthylamine disulfonic acids such, for example, as l-aminonaphthalene-3:6-disulionic acid, 1-aminonaphthalene-3:7-disulfonic acid, 1-aminonaphthalene-4:7edisulfonic acid or l-aminonaphthaleneg7-disulfonic acid. The arylamines to be used as coupling components and capable of couplingin para-position to the amino group maybelong, for example, to the. naphthalene series, but advantageously to the benzene series. As examples of such compounds here ma be ment ned; l'i millo-i rm y-be h lbenzene -dm nq -cfi oxy-5+methy1b' zene, learni o. IS-rnethylbenzene, l-aminoelie e h xv na cc zene, learnino z:5rdiethoxybenzene, 1-amino-.2 ethoxy+5emethoxybenzene, and as. examples of compounds of the naphthalene series: 1-amino-. naphthalene-fi-sulionic. acid, 1-aminonaphtha-.

lenes'l -sulfonic. acid or amixture of these two compounds, and. advantageously l-aminonaphthalene.

The 4-amino-4'-hydroxy- 1: 1'-azobenzene-3- carboxylic acids also to be used as starting materials may contain further substituents of the kind usually present in azo-dyestufis, such as halogen atoms, especially chlorine atoms, alkyl groups, especially methyl groups, and sulfonic ci g ps, S ch P QUP'Q ar i 31" genel" ally known, for; example, isaminolehydroxye 1:lGazobenzenefi'ecarbqxylic acid itself (see, for am le fi lteinz th edi i c p e 32 n a s s mmed-brewed arb w azobenzene-5'-sulfonic acid which may be used as a starting material (see Swiss Patent No. 2 9 3,692), or they can be made by methods in themselves known.

The linking of one molecular proportion of each ofethe two monoazo-dyestuffs to form the asymmetrical urea derivative is advantageously conducted ate. slightly, raised temperature in alkaline solution, advantageously in a solution rendered alkalinevvith an alkali carbonate.

The dyestuffs obtainable by the present il'lVBIl': 9

tion have a good affinity for vegetable fibers, and

are therefore, suitable. for dyeing or printing: cellulosic materials such aslinen, cotton and are tificialjsilk or staple fibers .ofregenerated cellulose. In, this manner there are obtained principally yellowto yellow-orange tints, which can generallybe discharged pure White by the neutral or alkaline dischargeprinting process.

1 amino=2:5 -dimethoxyben Especially valuable are those urea derivatives obtainable by the present invention which correspond to the formula 00011 R1 -N=NR, NH-l J-HN-R3-N=Niti-0H in which the radical R1 contains two sulfonic acid groups and the radicals R2, R3 and R4 are free from sulfonic acid groups.

If desired the dyestuffs may be treated in substance, on the fiber or in the dyebath with an agent yielding metal, for example, chromium, nickel, cobalt, manganese or iron and especially an agent yielding copper. Metallization in substance may be carried out in an alkaline, neutral or acid medium with or without the use of an addition favouring the formation of the complex or enhancing solubility. In many cases the treatment with an agent yielding metal, especially an agent yielding copper, is carried out with advantage on the fiber or in a single-bath process in 03H part in the dyebath and in part on the fiber, for example, in the manner described in U. S. Patent 2,148,659.

The following examples illustrate the invention, the parts being by weight:

Example 1 45.1 parts of the aminoazo-dyestufl', obtained by coupling diazotized l-aminonaphthalene-Bzfidisulfonic acid with 1 amino 2 methoxy methylbenzene, are dissolved together with 25.7 parts of 4-amino-4'-hydroxy-l:l-azobenzene 3-carboxylic acid in 4000 parts of water with the addition of sodium carbonate until a distinctly alkaline reaction is obtained, and the whole is treated, while stirring, at 30-35 C. with phosgene until free NHz-groups can no longer be detected. The resulting urea derivative of the formula HO S o-oH= 0 COOH is precipitated in the form of its sodium salt by means of sodium chloride, separated by filtration, and dried. It is a red-brown powder, which dissolves in water with a yellow coloration and dyes cotton orange-yellow tints. The dyeings are dis- HOrS tinguished by their good capacity for being discharged under neutral and alkaline conditions.

By using in this example, instead of l-amino- 2-methoxy-5-methylbenzene, 1-amino-2-ethoxy- 5-methylbenzene, and correspondingly using 46.5 parts of the aminoazo-dyestuff obtained by coupling diazotized 1-aminonaphthalene-3:6-disulfonic acid with 1-amino-2-ethoxy-5-methylbenzene, and in other respects following the procedure described above, there is obtained a dyestuff having very similar properties, which yields on cotton somewhat more reddish tints.

4 A dyestufl having similar properties is also obtained by treating with phosgene 45.1 parts of the aminoazo-dyestufi obtained by coupling diazotized 1-aminonaphthalene-3 G-disulfonic acid with 1-amino-2-methoxy-5-methylbenzene and 33.7 parts of 4-amino-4-hydroxy-1:1'-azobenzene-3'-carboxylic acid-5-sulfonic acid by the procedure described above.

Example 2 45.1 parts of the amonoazo-dyestufl, obtained by coupling diazotized l-aminonaphthalene-4:7- disulfonic acid with 1 amino 2 methoxy 5- methylbenzene, are dissolved with 25.7 parts of 4- amino 4 hydroxy 1:1 azobenzene-3'-car boxyllc acid in 4000 parts of water withthe addition of sodium carbonate until the reaction is distinctly alkaline, and the whole is treated while stirring with phosgene at -35 C. until NH:-

groups can no longer be detected. The resulting urea derivative of the formula H ac O-CHa COOH is precipitated in the form of its sodium salt by 1 means of sodium chloride, separated by filtration,

and dried. It is a red-brown powder, which dissolves in water with a yellow coloration and dyes cotton orange-yellow tints. The dyeings are characterized by a good capacity for being discharged under neutral and alkaline conditions.

By using in this example, instead of 1-amino-2- methoxy 5 methylbenzene, 1-amino-3-methylbenzene, and correspondingly using 42.1 parts of the aminoazo-dyestuff obtained by coupling diazotized 1 amino naphthalene 4:7-disulfonic acid with l-amino-S-methylbenzene, and in other respects following the procedure described above, there is obtained a dyestuif having similar properties which dyes cotton more yellow tints.

Example 3 45.7 parts of the amino-azo-dyestufi, obtained by coupling diazotized 1-aminonaphthalene-4z7- disulfonic acid with l-aminonaphthalene, are dissolved with 25.7 parts of 4-amino-4-hydroxy- 1:1-azobenzene-3'-carboxylic acid in 4000 parts of water with the addition of sodium carbonate until the reaction is distinctly alkaline, and the whole is treated with phosgene, while stirring at 30-35 C. until NHz-groups can no longer be detected. The resulting urea derivative of the formula C O OH is precipitated in the form of its sodium salt with the aid of sodium chloride, separated by filtration, and dried. It is a red-brown powder, which dissolves in water with a yellow coloration and dyes cotton orange-yellow tints. The dyeings are distinguished by their good capacity for being discharged under neutral and alkaline conditions.

Example 4 A dyebath is prepared with 1.2 parts of the dyestufi obtainable as described in the first par encased Parts Sodium formaldehyde sulfoxylate" 200 Water 120 British gum thickening, 1:1 550 Potassium carbonate 80 Glycerine 50 p 1000 What we claim is:--

1. An azo-dyestufi containing at least two sulfonic acid groups and corresponding to the general formula coon in whichRi stands for a naphthalene radical attachedto the azo group in an a-position and containing at least one sulfonic acid group but being otherwise free fromauxochromic groups, --R2-NH- standsfor the radical of an. aromatic amine selected from the group consisting of amines of the benzene and naphthalene series and coupled in para-position with respect to the amino group, and

stands for the radical of a 4-amino-4-hydroxy- 1: 1 -azobenzene-3 "-carboxylic 'acidi 2. Amazo-dyestufi corresponding to thegeneral formula in which R1 stands for a naphthalene radical attached to the azo group in an zx-DOSitiOIl and containing two sulfonic acid groups but being otherwise free from auxochromic groups, Rz--NH stands for the radical of an aromatic amine of the naphthalene series coupled in paraposition with respect to the amino group, and

stands for the radical of a 4-amino-4hydroxy- 1 :1 '-azobenzene-3-carboxylic acid.

3. An azo-dyestufi corresponding to the general formula H c 0 OH R1--N=NR2-NHo-HN R3 -N=N-in0H in which R1 stands for a naphthalene radical attached to the azo group in an zx-DOSitiOI] and containing two sulfonic acid groups but being otherwise free from auxochromic groups, -R2NH AWE stands for the radicalLoiraiizaroniaticranilnepf the naphthalene series coupled in para-positionwith respect to the amino group, and

00:03:- HN-RaN=l fRl0H stands for the radical of a 4-amino-4-h-y.droxy- 1:1'-azobenzene-3-carboxylic acid which is free.

from sulfonic acid groups. H

4. An azo-dyestuffcorrespondingto the general formula fir coo-H RlN N-"R-NH- o-HN Rg N=N-R.-on in which R1 stands for a naphthalene radical attached to the azo group in an (ii-position. and containing two sulfonic acid groups; but being otherwise free from auxochromic groups,.

stands for the radical of an amine of the benzene series being free from'sulfonicacid groupa-and coupled in para-position with respect to the.

1: 1'-azobienzene-3-carboirylic" acid which is free from sulfonic acid groups;

5. An azo-dyestufi corresponding to the general formula coon 0 I: i

in which R1 stands for a naphthaleneradical attached to the azo group in an u-position and containing two sulfonic acid groups but being free from auxochromic groups, and R2--NH stands for the radical of "an amine of thebenzene series being freefrom" sul'foniclacid groups and coupled in para-position" with respect to the amino group.

6. An azo-dyestufi corresponding to the general formula in which Rz-NH stands for the radical of an amine of the benzene series being free from sulfonic acid groups and coupled in para-position with respect to the amino group.

7. An azo-dyestuff corresponding to the general formula in which -R2NH- stands for the radical of an amine of the benzene series being free from sulfonic acid groups and coupled in para-position with respect to the amino group.

8. The azo-dyestuif of the formula HOsS OH OOOH O I ll 9. The azo-dyestufl of the formula.

H038 OCH:

10. The azo-dyestufl? of the formula OCH| COOH

COOH

i no... MQNHAHN MGOH BOgH 11. An azo-dyestuff corresponding to the general formula 0 00011 R N=N-R2NHg-HN-R N=N hOH in which R1 stands for a naphthalene radical attached to the azo group in an a-position and containing two sulfonic acid groups but being otherwise free from auxo-chromic groups, --R2-NH- stands for the radical of an aromatic amine of the benzene series coupled in paraposition with respect to the amino group, and

()OOH HNRzN=NR4-OH stands for the radical of a 4-amino-4'-hydroxy- 1: 1-azobenzene-3'-carboxylic acid.

12. An azo-dyestufi corresponding to the general formula OOOH O R,-N=N-R,-NH-t JHNRa-N=N-iu-o11 in which R1 stands for a naphthalene radical attached to the azo group in an a-position and containing two sulfonic acid groups but being otherwise free from auxo-chromic groups, R2-NH- stands for the radical of an aromatic amine of the benzene series coupled in para-position with respect to the amino group, and

stands for the radical of a 4-amino-4'-hydroxy- 1:1'-azobenzene-3'-carboxylic acid which is free from sulfonic acid groups.

OTTO KAISER. RAYMOND GUNST.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS 

